Dyeing composition with a lightening effect for human keratin materials comprising at least one fluorescent dye

ABSTRACT

The invention relates to a cosmetic dyeing composition that is used to lighten human keratinous matter and, more specifically, artificially colored or pigmented hair and dark skin. The inventive composition comprises at least one flourescent dye. The invention also relates to the methods using said composition.

The invention relates to a cosmetic composition for dyeing, with alightening effect, human keratin materials and more particularlyartificially dyed or pigmented hair and dark skin, comprising at leastone fluorescent dye. The invention also relates to the processes anddevice using these compositions.

It is common for individuals with dark skin to wish to lighten theirskin and for this purpose to use cosmetic or dermatological compositionscontaining bleaching agents.

The substances most commonly used as bleaching agent are hydroquinoneand its derivatives, kojic acid and its derivatives, azelaic acid,arbutin and its derivatives, alone or in combination with other activeagents.

However, these agents are not without their drawbacks. In particular,they need to be used for a long time and in large amounts in order toobtain a bleaching effect on the skin. No immediate effect is observedon applying compositions comprising them.

In addition, hydroquinone and its derivatives are used in an amount thatis effective to produce a visible bleaching effect. In particular,hydroquinone is known for its cytotoxicity toward melanocyte.

Moreover, kojic acid and its derivatives have the drawback of beingexpensive and consequently of not being able to be used in large amountin products for commercial mass distribution.

There is thus still a need for cosmetic compositions that allow alighter, uniform, homogeneous skin tone of natural appearance to beobtained, these compositions having satisfactory transparency afterapplication to the skin.

In the field of haircare, there are mainly two major types of hairdyeing.

The first is semi-permanent dyeing or direct dyeing, which uses dyescapable of giving the hair's natural color a more or less pronouncedmodification that withstands shampooing several times. These dyes areknown as direct dyes and may be used in two different ways. Thecolorations may be performed by applying the composition containing thedirect dye(s) directly to the keratin fibers, or by applying a mixture,prepared extemporaneously, of a composition containing the direct dye(s)with a composition containing an oxidizing bleaching agent, which ispreferably aqueous hydrogen peroxide solution. Such a process is thentermed “lightening direct dyeing”.

The second is permanent dyeing or oxidation dyeing. This is performedwith “oxidation” dye precursors, which are colorless or weakly coloredcompounds which, once mixed with oxidizing products, at the time of use,can give rise to colored compounds and dyes via a process of oxidativecondensation. It is often necessary to combine one or more direct dyeswith the oxidation bases and couplers in order to neutralize orattenuate the shades with too much of a red, orange or golden glint or,on the contrary, to accentuate these red, orange or golden glints.

Among the available direct dyes, nitrobenzene direct dyes are notsufficiently strong, and indoamines, quinone dyes and natural dyes havelow affinity for keratin fibers and consequently lead to colorationsthat are not sufficiently fast with respect to the various treatments towhich the fibers may be subjected, and in particular with respect toshampooing.

In addition, there is a need to obtain a lightening effect on humankeratin fibers. This lightening is conventionally obtained via a processof bleaching the melanins of the hair via an oxidizing system generallyconsisting of hydrogen peroxide optionally combined with persalts. Thisbleaching system has the drawback of degrading the keratin fibers and ofimpairing their cosmetic properties.

The Applicant thus investigated compounds that can provide solutions tothe problems mentioned above, i.e. that have good dyeing affinity forkeratin fibers, good fastness properties with respect to externalagents, and in particular with respect to shampooing, and that alsoallow lightening to be obtained without impairing the fiber.

As a result of these investigations, the Applicant has now discovered,surprisingly and unexpectedly, that the use of fluorescent dyes and inparticular those in the orange range allow these objectives to beachieved.

The literature discloses hair or skin compositions comprising opticalbrighteners or fluorescent brighteners, as described in Canadian patent1 255 603 or patent applications WO-99/13845 and WO-00/71085.Compositions for dyeing the hair with compounds that allow strong shadesto be obtained are also known, for instance those described in patentapplications WO-01/62759, DE-100 29 441 and DE-199 26 377. However,these compositions do not lighten the hair or the skin at the same timeas dyeing them.

Patent applications EP-0 370 470 and EP-0 445 342 describe cosmeticcompositions comprising an insoluble pigment that may be fluorescent(EP-0 370 470) formed by dissolving a dye in a resin. Such compositionsare not lightening.

Moreover, patents U.S. Pat. No. 5,356,438 and U.S. Pat. No. 5,188,639describe compositions for dyeing and conditioning the hair or for dyeingand permanent-waving the hair; however, they are not intended to lightenthe hair while dyeing it.

A first subject of the present invention is thus a cosmetic compositionfor dyeing human keratin materials with a lightening effect,characterized in that it comprises, in a cosmetically acceptable medium,at least one fluorescent dye that is soluble in the medium, whichre-emits the light that it has absorbed in the visible region and alsopossibly in the ultraviolet region of the spectrum, as fluorescent lightof a longer wavelength in the visible region of the spectrum.

For the purposes of the present invention, the term “fluorescent dye”means a dye which is a molecule that colors by itself, like anyconventional dye, and a dye which is soluble in the cosmetic medium andabsorbs light in the visible spectrum and possibly in the ultravioletspectrum (wavelengths ranging from 360 to 760 nanometers), but which, incontrast to a standard dye, converts the absorbed energy intofluorescent light of a longer wavelength emitted in the visible regionof the spectrum.

A fluorescent dye according to the invention is to be distinguished froman optical brightener. Optical brighteners, which are also known asbrighteners, fluorescent brighteners, fluorescent brightening agents,fluorescent whitening agents, whiteners or fluorescent whiteners, arecolorless transparent compounds, which do not dye because they do notabsorb light in the visible region, but only in the ultraviolet region(wavelengths ranging from 200 to 400 nanometers), and convert theabsorbed energy into fluorescent light of a longer wavelength emitted inthe visible region of the spectrum; the color impression is thengenerated solely by purely fluorescent light that is predominantly blue(wavelengths ranging from 400 to 500 nanometers).

According to the present invention, the term “human keratin materials”means the skin, the hair, the nails, the eyelashes and the eyebrows, andmore particularly dark skin and artificially colored or pigmented hair.

For the purposes of the invention, the term “dark skin” means a skinwhose lightness L* measured in the CIEL L*a*b* system is less than orequal to 45 and preferably less than or equal to 40, given that L*=0 isequivalent to black and L*=100 is equivalent to white. The skin typescorresponding to this lightness are African skin, afro-American skin,hispano-American skin, Indian skin and North African skin.

For the purposes of the invention, the expression “artificially dyed orpigmented hair” means hair whose tone height is less than or equal to 6(dark blond) and preferably less than or equal to 4 (chestnut-brown).

The lightening of the hair is evaluated by the “tone height”, whichcharacterizes the degree or level of lightening. The notion of “tone” isbased on the classification of the natural shades, one tone separatingeach shade from the shade immediately following or preceding it. Thisdefinition and the classification of the natural shades are well knownto hairstyling professionals and are published in the book “Sciences destraitements capillaires [Hair treatment sciences]” by Charles Zviak,1988, published by Masson, pp. 215 and 278.

The tone heights range from 1 (black) to 10 (light light blond), oneunit corresponding to one tone; the higher the figure, the lighter theshade.

The fluorescent dye according to the invention should be distinguishedfrom the fluorescent pigment. The pigment is insoluble in the medium,whereas the dye is soluble in the cosmetic medium at room temperature ofabout 15 to 25° C. In addition, the fluorescent dye according to theinvention is a dye that generates fluorescence on the cosmetic support.

A subject of the invention is, more particularly, a cosmetic compositionfor dyeing human keratin materials with a lightening effect,characterized in that it comprises, in a cosmetically acceptable medium,a sufficient amount of at least one fluorescent dye, such that, afterapplication to said materials, the composition gives a reflectance,measured at between 500 and 700 nm, which is higher than the reflectanceof said untreated keratin materials.

A subject of the invention is, more particularly, a cosmetic compositionfor dyeing, with a lightening effect, artificially dyed or pigmentedhair with a tone height of less than or equal to 6 and preferably lessthan or equal to 4, and also characterized in that it comprises, in acosmetically acceptable medium, a sufficient amount of at least onefluorescent dye, such that, after application to the hair, thecomposition gives a reflectance, measured at between 500 and 700 nm,which is at least 0.05% and preferably at least 0.1% higher than thereflectance of the untreated hair.

Such a composition according to the invention has the advantage oflightening the hair without degrading it and of simultaneously dyeingit.

According to the present invention, the fluorescent dye, which isoptionally neutralized, is soluble in the cosmetic medium to at leastone gram per liter and preferably to at least five grams per liter at atemperature of 25° C.

Preferably, according to the invention, the fluorescent dye is not afluorescein dye or a xanthene derivative as described in patentapplication DE-199 26 377, or a cyclopentaquinoxalinium compound asdescribed in patent application DE-100 29 441, since these compounds arenot without toxicology.

In addition, and preferably, the composition according to the inventionis capable of lightening the hair and the skin in a shade which,measured in the CIEL L*a*b* system, has a variable b* of greater than orequal to 6, with a b*/absolute value of a* ratio of greater than 1.2according to the selection test described below.

Selection Test

The composition is applied to chestnut-brown hair, at a rate of 10 gramsof composition per 1 gram of chestnut-brown hair. The composition isspread on so as to cover all of the hair. The composition is left to actfor 20 minutes at room temperature (20 to 25° C.). The fibers are thenrinsed with water and then washed with a shampoo based on lauryl ethersulfate. They are then dried. The spectrocolorimetric characteristics ofthe hair are then measured in order to determine the L*a*b* coordinates.

In the CIEL L*a*b* system, a* and b* indicate two color axes: a*indicates the green/red color axis (+a* is red, −a* is green) and b*indicates the blue/yellow color axis (+b* is yellow and −b* is blue);values close to zero for a* and b* correspond to gray shades.

The fluorescent dyes preferably used according to the present inventionare dyes in the orange range.

Preferably, after application to the hair, for example chestnut-brownhair, the composition should give the following results:

Attention is focused on the reflectance qualities of the hair when it isirradiated with visible light in the wavelength range from 400 to 700nanometers.

Thus, the curves of reflectance as a function of the wavelength arecompared for hair treated with the composition of the invention anduntreated hair. The curve corresponding to the treated hair should showa reflectance in the wavelength range from 500 to 700 nanometers that ishigher than the curve corresponding to the untreated hair.

This means that, in the wavelength range from 540 to 700 nanometers,there is at least one range in which the reflectance curve correspondingto the treated hair is higher than the reflectance curve correspondingto the untreated hair.

The term “higher than” means a difference of at least 0.05% andpreferably of at least 0.1% of reflectance. This does not prevent thepossibility of existence, in the wavelength range from 540 to 700nanometers, of at least one region in which the reflectance curvecorresponding to the treated hair is superimposable or lower than thereflectance curve corresponding to the untreated hair.

Preferably, the wavelength at which the difference is maximal betweenthe reflectance curve for the treated hair and that for the untreatedhair is in the wavelength range from 500 to 650 nanometers andpreferably in the wavelength range from 550 to 620 nanometers.

A subject of the invention is also the use of a fluorescent dye as alightening and dyeing agent in, or for the manufacture of, a cosmeticcomposition as defined above, to lighten while dyeing human keratinmaterials, in particular dark skin and more particularly artificiallydyed or pigmented hair.

The fluorescent dyes according to the present invention are known andcommercialized compounds.

Mention may especially be made among these dyes of:

-   the Photosensitizing Dye NK-557 sold by the company Ubichem, which    has the following structure:

2-[2-(4-dimethylamino)phenylethenyl]-1-ethylpyridinium iodide;

-   Brilliant Yellow B6GL sold by the company Sandoz and having the    following structure:

-   Basic Yellow 2, or Auraminoe 0, sold by the companies Prolabo,    Aldrich or Carlo Erba and having the following structure:

4,4′-(imidocarbonyl)bis(N,N-dimethylaniline)monohydro-chloride —CASnumber 2465-27-2.

The fluorescent dye(s) of the present invention preferably represent(s)from 0.01% to 20%, more preferably from 0.05% to 10% and even moreparticularly from 0.1% to 5% by weight approximately relative to thetotal weight of the composition.

The cosmetically acceptable medium generally consists of water or of amixture of water and of at least one organic solvent.

Examples of organic solvents that may be mentioned include C₁–C₄ loweralkanols such as ethanol and isopropanol; glycerol; glycols and glycolethers, for instance 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monomethyl ether and monoethylether, and also aromatic alcohols, for instance benzyl alcohol orphenoxyethanol, similar products and mixtures thereof.

The solvents may be present in proportions preferably ranging from 1% to40% by weight approximately and even more preferably from 5% to 30% byweight approximately relative to the total weight of the dyecomposition.

The pH of the composition in accordance with the invention is generallybetween 3 and 12 approximately and preferably between 5 and 11approximately. It may be adjusted to the desired value by means ofacidifying or basifying agents usually used in the dyeing of humankeratin fibers.

Examples of acidifying agents that may be mentioned include mineral ororganic acids, for instance hydrochloric acid, orthophosphoric acid,sulfuric acid, carboxylic acids, for instance acetic acid, tartaricacid, citric acid and lactic acid, and sulfonic acids.

Examples of basifying agents that may be mentioned include aqueousammonia, alkaline carbonates, alkanolamines such as monoethanolamine,diethanolamine and triethanolamine and derivatives thereof, sodiumhydroxide, potassium hydroxide and the compounds of formula (I) below:

in which W is a propylene residue optionally substituted with a hydroxylgroup or a C₁–C₆ alkyl radical; R₁, R₂, R₃ and R₄, which may beidentical or different, represent a hydrogen atom or a C₁–C₆ alkyl orC₁-C₆ hydroxyalkyl radical.

According to one preferred embodiment, the cosmetic composition inaccordance with the invention may comprise, in addition to thefluorescent dye(s), one or more additional direct dyes of nonionic,cationic or anionic nature, which may be chosen, for example, from thefollowing red or orange nitrobenzene dyes:

-   1-hydroxy-3-nitro-4-N-(γ-hydroxypropyl)aminobenzene,-   N-(β-hydroxyethyl)amino-3-nitro-4-aminobenzene,-   1-amino-3-methyl-4-N-(β-hydroxyethyl)amino-6-nitrobenzene,-   1-hydroxy-3-nitro-4-N-(β-hydroxyethyl)aminobenzene,-   1,4-diamino-2-nitrobenzene,-   1-amino-2-nitro-4-methylaminobenzene,-   N-(β-hydroxyethyl)-2-nitro-para-phenylenediamine,-   1-amino-2-nitro-4-(β-hydroxyethyl)amino-5-chlorobenzene,-   2-nitro-4-aminodiphenylamine,-   1-amino-3-nitro-6-hydroxybenzene,-   1-(β-aminoethyl)amino-2-nitro-4-(β-hydroxyethyloxy)-benzene,-   1-(β,γ-dihydroxypropyl)oxy-3-nitro-4-(β-hydroxyethyl)-aminobenzene,-   1-hydroxy-3-nitro-4-aminobenzene,-   1-hydroxy-2-amino-4,6-dinitrobenzene,-   1-methoxy-3-nitro-4-(β-hydroxyethyl)aminobenzene,-   2-nitro-4′-hydroxydiphenylamine and-   1-amino-2-nitro-4-hydroxy-5-methylbenzene.

The cosmetic composition in accordance with the invention may alsocomprise, in addition to or in replacement for these nitrobenzene dyes,one or more additional direct dyes chosen from yellow, green-yellow,blue or violet nitrobenzene dyes, azo dyes, anthraquinone dyes,naphthoquinone dyes, benzoquinone dyes, indigoid dyes, andtriarylmethane-based dyes.

These additional direct dyes may especially be basic dyes, among whichmention may be made more particularly of the dyes known in the ColorIndex, 3rd edition, under the names “Basic Brown 16”, “Basic Brown 17”,“Basic Yellow 57”, “Basic Red 76”, “Basic Violet 10”, “Basic Blue 26”and “Basic Blue 99”, or acidic direct dyes, among which mention may bemade more particularly of the dyes known in the Color Index, 3rdedition, under the names “Acid Orange 7”, “Acid Orange 24”, “Acid Yellow36”, “Acid Red 33”, “Acid Red 184”, “Acid Black 2”, “Acid Violet 43” and“Acid Blue 62”, or alternatively cationic direct dyes such as thosedescribed in WO 95/01772, WO 95/15144 and EP-A-0 714 954, the content ofwhich forms an integral part of the present invention.

Among the additional yellow and green-yellow nitrobenzene direct dyesthat may be mentioned, for example, are the compounds chosen from:

-   1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene,-   1-methylamino-2-nitro-5-(β,γ-dihydroxypropyl)oxybenzene,-   1-(β-hydroxyethyl)amino-2-methoxy-4-nitrobenzene,-   1-(β-aminoethyl)amino-2-nitro-5-methoxybenzene,-   1,3-di(β-hydroxyethyl)amino-4-nitro-6-chlorobenzene,-   1-amino-2-nitro-6-methylbenzene,-   1-(β-hydroxyethyl)amino-2-hydroxy-4-nitrobenzene,-   N-(β-hydroxyethyl)-2-nitro-4-trifluoromethylaniline,-   4-(β-hydroxyethyl)amino-3-nitrobenzenesulfonic acid,-   4-ethylamino-3-nitrobenzoic acid,-   4-(β-hydroxyethyl)amino-3-nitrochlorobenzene,-   4-(β-hydroxyethyl)amino-3-nitromethylbenzene,-   4-(β,γ-dihydroxypropyl)amino-3-nitrotrifluoromethylbenzene,-   1-(β-ureidoethyl)amino-4-nitrobenzene,-   1,3-diamino-4-nitrobenzene,-   1-hydroxy-2-amino-5-nitrobenzene,-   1-amino-2-[tris(hydroxymethyl)methyl]amino-5-nitrobenzene,-   1-(β-hydroxyethyl)amino-2-nitrobenzene and-   4-(β-hydroxyethyl)amino-3-nitrobenzamide.

Among the additional blue or violet nitrobenzene direct dyes that may bementioned, for example, are the compounds chosen from:

-   1-(β-hydroxyethyl)amino-4-N,N-bis(β-hydroxyethyl)amino-2-nitrobenzene,-   1-(γ-hydroxypropyl)amino-4,N,N-bis(β-hydroxyethyl)amino-2-nitrobenzene,-   1-(β-hydroxyethyl)amino-4-(N-methyl-N-β-hydroxy-ethyl)amino-2-nitrobenzene,-   1-(β-hydroxyethyl)amino-4-(N-ethyl-N-β-hydroxyethyl)amino-2-nitrobenzene,-   1-(β,γ-dihydroxypropyl)amino-4-(N-ethyl-N-β-hydroxy-ethyl)amino-2-nitrobenzene,-   2-nitro-para-phenylenediamines having the following formula (II):

-    in which:    -   R₆ represents a C₁–C₄ alkyl radical or a β-hydroxy-ethyl,        β-hydroxypropyl or γ-hydroxypropyl radical;    -   R₅ and R₇, which may be identical or different, represent a        β-hydroxyethyl, β-hydroxypropyl, γ-hydroxypropyl or        β,γ-dihydroxypropyl radical, at least one of the radicals R₆, R₇        or R₅ representing a γ-hydroxypropyl radical and R₆ and R₇ not        simultaneously being able to denote a β-hydroxyethyl radical        when R₆ is a γ-hydroxypropyl radical, such as those described in        FR 2 692 572.

When they are present, the additional direct dye(s) preferablyrepresent(s) from 0.0005% to 12% by weight approximately relative to thetotal weight of the composition, and even more preferably from 0.005% to6% by weight approximately relative to this weight.

When it is intended for oxidation dyeing, the cosmetic composition inaccordance with the invention comprises, in addition to the fluorescentcompound(s), at least one oxidation base chosen from the oxidation basesconventionally used for oxidation dyeing and among which mention may bemade especially of para-phenylenediamines, bis(phenyl)alkylenediamines,para-aminophenols, ortho-aminophenols and heterocyclic bases, and theaddition salts thereof with an acid or with an alkaline agent.

Among the para-phenylenediamines that may be mentioned moreparticularly, for example, are para-phenylenediamine,para-tolylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine and4′-aminophenyl-1-(3-hydroxy)pyrrolidine, and the addition salts thereofwith an acid or with an alkaline agent.

Among the para-phenylenediamines mentioned above, the ones mostparticularly preferred are para-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid or with an alkaline agent.

Among the bis(phenyl)alkylenediamines that may be mentioned moreparticularly, for example, areN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetra-methylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition saltsthereof with an acid or with an alkaline agent.

Among the para-aminophenols that may be mentioned more particularly, forexample, are para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts thereof with an acid or with an alkaline agent.

Among the ortho-aminophenols that may be mentioned more particularly,for example, are 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the additionsalts thereof with an acid or with an alkaline agent.

Among the heterocyclic bases that may be mentioned more particularly,for example, are pyridine derivatives, pyrimidine derivatives andpyrazole derivatives, and the addition salts thereof with an acid orwith an alkaline agent.

When they are used, the oxidation base(s) advantageously represent(s)from 0.0005% to 12% by weight relative to the total weight of thecomposition and even more preferably from 0.005% to 6% by weightapproximately relative to this weight.

When it is intended for oxidation dyeing, the cosmetic composition inaccordance with the invention may also comprise, in addition to thefluorescent dyes and the oxidation bases, at least one coupler so as tomodify or to enrich with glints the shades obtained using thefluorescent dyes and the oxidation base(s).

The couplers that may be used in the cosmetic composition in accordancewith the invention may be chosen from the couplers conventionally usedin oxidation dyeing, and among which mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers, and the addition salts thereof with an acid orwith an alkaline agent.

These couplers are more particularly chosen from 2-methyl-5-aminophenol,5-N-(5-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxy-benzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole and6-methylpyrazolo[1,5-a]benzimidazole, and the addition salts thereofwith an acid or with an alkaline agent.

When they are present, the coupler(s) preferably represent(s) from0.0001% to 10% by weight and even more preferably from 0.005% to 5% byweight relative to the total weight of the composition.

In general, the addition salts with an acid that may be used in thecontext of the compositions of the invention (oxidation bases andcouplers) are chosen especially from the hydrochlorides, hydrobromides,sulfates, citrates, succinates, tartrates, tosylates, benzenesulfonates,lactates and acetates.

The addition salts with an alkaline agent that may be used in thecontext of the compositions of the invention (oxidation bases andcouplers) are chosen especially from the addition salts with alkalimetals or alkaline-earth metals, with ammonia and with organic amines,including alkanolamines and the compounds of formula (I).

The cosmetic composition in accordance with the invention may alsocomprise various adjuvants conventionally used in cosmetic compositions,in particular for dyeing human keratin fibers, such as anionic,cationic, nonionic, amphoteric or zwitterionic surfactants or mixturesthereof, anionic, cationic, nonionic, amphoteric or zwitterionicpolymers, or mixtures thereof, mineral or organic thickeners,antioxidants, penetrating agents, sequestering agents, fragrances,buffers, dispersants, conditioners, for instance cations, cationic oramphoteric polymers, volatile or nonvolatile, modified or unmodifiedsilicones, film-forming agents, ceramides, preserving agents,stabilizers and opacifiers.

Among the thickeners that it is more particularly preferred to use arethickening systems based on associative polymers that are well known tothose skilled in the art and especially of nonionic, anionic, cationicor amphoteric nature.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compound(s) such that the advantageousproperties intrinsically associated with the composition in accordancewith the invention are not, or are not substantially, adversely affectedby the envisaged addition(s).

The cosmetic composition according to the invention may be in variousforms, such as in the form of liquids, shampoos, creams or gels, or inany other suitable form.

One form that is particularly preferred according to the presentinvention, and which constitutes another subject of the invention, is alightening and dyeing shampoo comprising, in a cosmetically acceptableaqueous medium, at least one fluorescent dye as defined above, and atleast one surfactant, which is preferably nonionic.

In these shampoos, the surfactants are present in a proportion rangingfrom about 4% to 30% and preferably from about 8% to 20% by weightrelative to the total weight of the shampoo composition, and thenonionic surfactants that are more particularly preferred are chosenfrom alkylpolyglucosides.

In the composition according to the invention, when one or moreoxidation bases are used, optionally in the presence of one or morecouplers, or when the fluorescent dye(s) is (are) used in the context ofa lightening direct dyeing operation, then the composition in accordancewith the invention may also contain at least one oxidizing agent chosen,for example, from hydrogen peroxide, urea peroxide, alkali metalbromates, persalts such as perborates and persulfates, and enzymes suchas peroxidases and two-electron or four-electron oxidoreductases. Theuse of hydrogen peroxide or of enzymes is particularly preferred.

Another subject of the invention is a process for dyeing and lighteningthe hair, using a composition as defined above, in the absence ofoxidation dyes and of oxidizing agents.

Another subject of the invention is a process for dyeing the hair usinga composition as defined above, in the absence of oxidation dyes but inthe presence of oxidizing agents.

According to a first variant of these dyeing processes in accordancewith the invention, at least one composition as defined above is appliedto the hair, for a time that is sufficient to develop the desiredcoloration and lightening, after which the hair is rinsed, optionallywashed with shampoo, rinsed again and dried.

According to a second variant of these dyeing processes in accordancewith the invention, at least one composition as defined above is appliedto the hair, for a time that is sufficient to develop the desiredcoloration and lightening, without final rinsing.

According to a third variant of the dyeing process in accordance withthe invention, the dyeing process comprises a preliminary step thatconsists in separately storing, on the one hand, a compositioncomprising, in a medium that is suitable for dyeing, at least onefluorescent dye, and, on the other hand, a composition comprising, in amedium that is suitable for dyeing, at least one oxidizing agent, andthen in mixing them together at the time of use, followed by applyingthis mixture to the hair for a time that is sufficient to develop thedesired coloration, after which the hair is rinsed, optionally washedwith shampoo, rinsed again and dried.

Another subject of the invention is a process for the oxidation dyeingof the hair using a composition as defined above in the presence ofoxidation dyes.

According to this dyeing process, the dyeing process comprises apreliminary step that consists in separately storing, on the one hand, acomposition comprising, in a medium that is suitable for dyeing, atleast one fluorescent dye and at least one oxidation base, and, on theother hand, a composition comprising, in a medium that is suitable fordyeing, at least one oxidizing agent, and then in mixing them togetherat the time of use, followed by applying this mixture to the hair for atime that is sufficient to develop the desired coloration, after whichthe hair is rinsed, optionally washed with shampoo, rinsed again anddried.

Another subject of the invention is a multi-compartment device fordyeing and lightening the hair, comprising at least one compartmentcontaining a composition comprising at least one fluorescent dye, and atleast one other compartment containing a composition comprising at leastone oxidizing agent. This device may be equipped with a means forapplying the desired mixture to the hair, such as the devices describedin patent FR-2 586 913 in the name of the Applicant.

A subject of the invention is also a process that consists in applyingthe composition according to the invention to hair with a tone height ofless than or equal to 6 and preferably less than or equal to 4.

The time required to develop the coloration and to obtain the lighteningeffect on the hair is from about 5 to 60 minutes and more particularlyfrom about 5 to 40 minutes.

The temperature required to develop the coloration and to obtain thelightening effect on the hair is generally between room temperature (15to 25° C.) and 80° C. and more particularly between 15 and 40° C.

Another subject of the invention is a process for lightening skin whoselightness L* in the CIEL L*a*b* system is less than or equal to 45 andpreferably less than or equal to 40, which consists in applying to theskin a composition in accordance with the invention and as describedabove.

The examples that follow are intended to illustrate the inventionwithout, however, limiting its scope.

EXAMPLES 1 to 5

The 3 direct dyeing compositions below according to the invention wereprepared (contents in grams):

EXAMPLES according to the invention 1 2 3 Fluorescent dye NK-557 0.5 —Fluorescent dye Brilliant Yellow B6GL 0.5 Fluorescent dye Basic Yellow 20.5 Hydroxyethylcellulose 1.6 1.6 1.6 (50/50 C8/C10)alkyl polyglucosideas a 6 AM* 6 AM* 6 AM* buffered 60% aqueous solution Benzyl alcohol 8 88 Polyethylene glycol 12 12 12 Mixture of methyl, butyl, ethyl, 0.120.12 0.12 propyl and isobutyl p-hydroxybenzoates Demineralized water qs100 100 100 AM* denotes Active Material

Two comparative compositions, not in accordance 15 with the invention,having the same composition as the above three compositions according tothe invention, with the exception of the dye, which is also orange butis non-fluorescent, were also prepared:

Comparative Examples not in accordance with the invention 4 5Non-fluorescent dye ♦ 0.5 Non-fluorescent dye ♦♦ 0.5Hydroxyethylcellulose 1.6 1.6 (50/50 C8/C10)alkyl polyglucoside as a 6AM* 6 AM* buffered 60% aqueous solution Benzyl alcohol 8 8 Polyethyleneglycol 12 12 Mixture of methyl, butyl, ethyl, 0.12 0.12 propyl andisobutyl p-hydroxybenzoates Demineralized water qs 100 100 AM* denotesActive Material ♦ 2-nitro-4-hydroxy-1-aminobenzene ♦♦ Basic Orange 31 orVibracolor flame orange sold by the company Ciba Geigy, having thefollowing formula:

Each composition 1 to 5 was applied, at a rate of 10 grams each, to 1 gof locks of chestnut-brown natural hair and was left to act for 20minutes. The locks were then rinsed with water and then dried.

After 24 hours, the locks were read using a Minolta CM 2002 calorimeterin the L*A*b* system, and the tone heights were evaluated.

The results are collated in table (I) below:

TH* L* a* b* b*/a* Non-dyed control 4 24.24 3.82 4.51 1.18 Composition 15 26.77 5.61 8.41 1.50 Composition 2 4.5 25.85 −1.07 8.92 8.34Composition 3 5 24.76 1.61 6 3.73 Composition 4 4 23.99 6.43 5.71 0.89Composition 5 4 23.25 6.84 4.44 0.65 TH* denotes Tone Height

From these results it is clearly seen that only the three compositions 1to 3 according to the invention color the hair while lightening it.

Moreover, the differences in reflectance between the untreatedchestnut-brown hair and the chestnut-brown hair treated with each of theabove compositions 1 to 5 were as follows:

Wavelength in Difference in Composition nanometers reflectance, in % 1580 1.49 2 550 0.17 3 550 0.33 4 550 −0.38 5 550 −0.66

The results are given on the reflectance curves table (II) below.

This graph shows on the x-axis the wavelength of the light illuminatingthe hair, and on the y-axis the difference in reflectance of the hairfor each wavelength between the dyed chestnut-brown hair and thenon-dyed chestnut-brown hair (tone height 4).

It is noted that, for compositions 1, 2 and 3 (with fluorescent dyes),the reflectance is positive (>0%) throughout virtually all thewavelength range, whereas, for compositions 4 and 5 (withnon-fluorescent dyes), the reflectance is always negative and thus lowerthan the reflectance of the non-dyed chestnut-brown hair.

EXAMPLE 6

The lightening and dyeing shampoo of the composition below was prepared:

(contents expressed in grams of Active Material AM*)

Nonionic surfactant: alkyl polyglucoside as an 15.9 AM* aqueous solutioncontaining 53% AM* (Plantacare 2002 Up sold by Cognis 1,2-Pentanediol0.1 Glycerol 7 Anisic acid 0.2 Cationic conditioner: Quaternium-87 0.15AM* (dimethylalkylamidoethylimidazolium methosulfate as a solution inpropylene glycol or Rewoquat W 575 PG sold by Goldschmidt) Stabilizer:polyethylene glycol distearate (PEG- 4.2 50 distearate) Sodium chloride3 Citric acid 2.4 Sodium hydroxide 0.92 Fluorescent dye NK-557 0.5Demineralized water qs 100

Five tests of application of this shampoo to locks of chestnut-brownhair were then performed by applying the selection test described in theinvention.

Tests 3 and 4 were performed to show that the shampoos can besuperimposed and nevertheless lead to a simultaneous lightening anddyeing result.

-   Test 1: a lock of 1 gram of chestnut-brown hair was treated with 10    grams of shampoo for 20 minutes at room temperature. The lock was    then rinsed with water and dried.-   Test 2: a lock of 1 gram of chestnut-brown hair was treated with 0.4    gram of shampoo for one minute at room temperature. The lock was    then rinsed with water and dried.-   Test 3: the 1-gram lock of hair from Test 2 was again treated with    0.4 gram of shampoo for one minute at room temperature. The lock was    then rinsed with water and dried.-   Test 4: the 1-gram lock of hair from Test 3 was again treated with    0.4 gram of shampoo for one minute at room temperature. The lock was    then rinsed with water and dried.

The locks were lightened, and the L*a*b* measurements collated in table(III) below show that the composition of example 6 satisfies theselection criteria of the present invention.

TABLE (III) Difference Wavelength in b*/absolute in reflectance L* a* b*value of a* nanometers in % Control** 22.34 3.14 3.96 Test 1 23.86 4.187.48 1.79 580 0.84 Test 2 23.98 3.72 6.24 1.68 580 0.74 Test 3 23.843.91 6.15 1.57 580 0.74 Test 4 24.33 4.26 7.13 1.67 580 1.04 **untreatedhair

1. A process for dyeing hair having a tone height of less than or equalto 6 with a lightening effect, comprising applying to the hair, in anamount effective to provide a lightening effect on fibers that have atone height of less than or equal to 6, a composition comprising, in acosmetically acceptable medium, at least one fluorescent dye that issoluble in the cosmetically acceptable medium, which re-emits light thatit has absorbed in the visible region of the spectrum as fluorescentlight of a longer wavelength in the visible region of the spectrum;wherein the at least one fluorescent dye is chosen from:


2. The process according to claim 1, wherein the at least onefluorescent dye re-emits, in addition to the light that it has absorbedin the visible region of the spectrum, the light that it has absorbed inthe ultraviolet region of the spectrum as fluorescent light of a longerwavelength in the visible region of the spectrum.
 3. The processaccording to claim 1, wherein the hair is artificially dyed or pigmentedhair.
 4. The process according to claim 1, wherein the hair has a toneheight of less than or equal to
 4. 5. The process according to claim 1,wherein the at least one fluorescent dye is present in an amount suchthat, after application to the hair, the composition gives areflectance, ranging from 500 to 700 nm, which is at least 0.05% higherthan the reflectance of the hair not treated with the composition. 6.The process according to claim 5, wherein the at least one fluorescentdye is present in an amount such that, after application to the hair,the composition gives a reflectance, ranging from 500 to 700 nm, whichis at least 0.1% higher than the reflectance of the hair not treatedwith the composition.
 7. The process according to claim 1, wherein theat least one fluorescent dye lightens the hair and the skin in a shadewhich, measured in the CIEL L*a*b* system, has a variable b* of greaterthan or equal to 6, with a b*/absolute value of a* ratio of greater than1.2.
 8. The process according to claim 1, wherein the at least onefluorescent dye is present in an amount ranging from 0.01% to 20% byweight, relative to the total weight of the composition.
 9. The processaccording to claim 8, wherein the at least one fluorescent dye ispresent in an amount ranging from 0.05% to 10% by weight, relative tothe total weight of the composition.
 10. The process according to claim9, wherein the at least one fluorescent dye is present in an amountranging from 0.1% to 5% by weight, relative to the total weight of thecomposition.
 11. The process according to claim 1, wherein thecosmetically acceptable medium comprises water or a mixture of water andof at least one organic solvent.
 12. The process according to claim 1,wherein the composition has a pH ranging from 3 to
 12. 13. The processaccording to claim 12, wherein the composition has a pH ranging from 5to
 11. 14. The process according to claim 1, wherein the compositionfurther comprises at least one additional direct dye chosen fromnonionic, cationic, and anionic direct dyes.
 15. The process accordingto claim 14, wherein the at least one additional direct dye is chosenfrom nitrobenzene dyes.
 16. The process according to claim 14, whereinthe at least one additional direct dye is chosen from azo dyes,anthraquinone dyes, naphthoquinone dyes, benzoquinone dyes, indigoiddyes and triarylmethane-based dyes.
 17. The process according to claim14, wherein the at least one additional direct dye is present in anamount ranging from 0.0005% to 12% by weight, relative to the totalweight of the composition.
 18. The process according to claim 17,wherein the at least one additional direct dye is present in an amountranging from 0.005% to 6% by weight, relative to the total weight of thecomposition.
 19. The process according to claim 1, wherein thecomposition is in the form of a lightening and dyeing shampoo, andfurther comprises at least one surfactant.
 20. The process according toclaim 19, wherein the at least one surfactant is nonionic.
 21. Theprocess according to claim 1, wherein the composition is an oxidationdyeing composition and comprises at least one oxidation base.
 22. Theprocess according to claim 21, wherein the at least one oxidation baseis chosen from para-phenylenediamines, bis(phenyl)alkylenediamines,para-aminophenols, ortho-aminophenols and heterocyclic bases, and theaddition salts thereof with an acid or with an alkaline agent.
 23. Theprocess according to claim 22, wherein the at least one oxidation baseis present in an amount ranging from 0.0005% to 12% by weight, relativeto the total weight of the composition.
 24. The process according toclaim 23, wherein the at least one oxidation base is present in anamount ranging from 0.005% to 6% by weight, relative to the total weightof the composition.
 25. The process according to claim 21, wherein thecomposition further comprises at least one coupler chosen frommeta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers, and addition salts thereof with an acid or withan alkaline agent.
 26. The process according to claim 25, wherein the atleast one coupler is present in an amount ranging from 0.0001% to 10% byweight, relative to the total weight of the dye composition.
 27. Theprocess according to claim 26, wherein the at least one coupler ispresent in an amount ranging from 0.005% to 5% by weight, relative tothe total weight of the dye composition.
 28. The process according toclaim 1, wherein the composition further comprises at least oneoxidizing agent.
 29. The process according to claim 28, wherein the atleast one oxidizing agent is chosen from hydrogen peroxide, ureaperoxide, alkali metal bromates, persalts, and enzymes.
 30. The processaccording to claim 29, wherein the persalts are chosen from perboratesand persulfates.
 31. The process according to claim 29, wherein theenzymes are chosen from peroxidases and two-electron and four-electronoxidoreductases.
 32. The process according to claim 29, wherein theoxidizing agent is hydrogen peroxide.
 33. A multi-compartment device fordyeing and lightening the hair, comprising at least one firstcompartment comprising at least one cosmetic composition for dyeing hairhaving a tone height of less than or equal to 6 with a lighteningeffect, comprising, in a cosmetically acceptable medium, at least onefluorescent dye that is soluble in the cosmetically acceptable medium,which re-emits light that it has absorbed in the visible region of thespectrum as fluorescent light of a longer wavelength in the visibleregion of the spectrum, and comprising at least one second compartmentcomprising at least one composition comprising at least one oxidizingagent; wherein the at least one fluorescent dye is chosen from:


34. The device according to claim 33, wherein the at least onefluorescent dye re-emits, in addition to the light that it has absorbedin the visible region of the spectrum, the light that it has absorbed inthe ultraviolet region of the spectrum as fluorescent light of a longerwavelength in the visible region of the spectrum.